过渡金属,Zr,Ce三元SCR催化剂的制备和性能*

doi:10.11901/1005.3093.2015.088

材料研究学报

2016, Vol. 30

Issue (2): 123-130 DOI: 10.11901/1005.3093.2015.088

本期目录 | 过刊浏览

过渡金属,Zr,Ce三元SCR催化剂的制备和性能*

刘海弟(

), 李伟曼, 李文辉, 陈运法

中国科学院过程工程研究所多相复杂系统国家重点实验室北京 100190

Preparation and Characterization of Ternary SCR Catalysts Consisted of Transition Metal Oxide, Zirconia and Ceira

LIU Haidi^**(

), LI Weiman, LI Wenhui, CHEN Yunfa

(State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China)

引用本文:

刘海弟, 李伟曼, 李文辉, 陈运法. 过渡金属,Zr,Ce三元SCR催化剂的制备和性能*[J]. 材料研究学报, 2016, 30(2): 123-130.
Haidi LIU, Weiman LI, Wenhui LI, Yunfa CHEN. Preparation and Characterization of Ternary SCR Catalysts Consisted of Transition Metal Oxide, Zirconia and Ceira[J]. Chinese Journal of Materials Research, 2016, 30(2): 123-130.

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摘要:

制备了由过渡金属M(M=Cr,Mn,V,Fe,Cu,Co)与Zr,Ce氧化物组成的三元选择性催化还原(SCR)催化剂, 用低温氮吸附(BET),X射线衍射分析(XRD),X射线光电子能谱(XPS),氨-程序升温脱附(NH₃-TPD),氢-程序升温还原(H₂-TPR)等手段表征了样品的比表面和孔结构,晶体结构,元素价态,酸性位类型以及氧化还原能力, 研究了催化剂的性能.结果表明, Mn-Zr-Ce三元催化剂的低温(<200℃)活性较好, 但是高温(>250℃)活性较差; Cr-Zr-Ce三元催化剂在低温和高温(100-300℃)下性能均比较稳定, V-Zr-Ce三元催化剂在低温(<200℃)下性能较差, 但是其高温(300℃左右)活性不断提高.研究了以上3种催化剂的耐硫性, 并结合测试结果解释和分析了上述实验现象.

关键词 ：无机非金属材料, 氧化铈, 氧化锆, 过渡金属, 氮氧化物, 选择性催化还原

Abstract：

Ternary selective catalytic reduction (SCR) catalysts composed of transition metal oxide M_xO_y (M=Cr, Mn, V, Fe, Cu, Co), zirconia and ceria were prepared. The catalysts were characterized in terms of surface area, pore structure, crystal structure, element valence state, type of acidic sites and redox ability and catalytical properties by means of low-temperature N₂ adsorption (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), NH₃-temperature programmed desorption (NH₃-TPD) and H₂-temperature programmed reduction (H₂-TPR) methods. The results show that the ternary catalyst of Mn-Zr-Ce oxides exhibited good low-temperature (<200℃) activity, but poor high-temperature (>250℃) activity. The ternary catalyst of Cr-Zr-Ce oxides showed good and stable activity in the whole temperature range 100-300℃. The ternary catalyst of V-Zr-Ce oxides was very poor in catalyzing the SCR reaction at low temperature (<200℃), but exhibited better performance at high temperature (around 300℃). The sulphur-tolerance of the as-made samples were also investigated. All the phenomena observed were explained on the basis of the characterization results of the as-made samples.

Key words： inorganic non-metallic materials ceria zirconia transition metal NOx SCR

收稿日期: 2015-02-15

ZTFLH:

TB321

基金资助:* 中国科学院先导专项B(XDB05050400), 国家自然科学基金21107111和中国科学院知识创新工程重要方向项目KZCX2-EW-403资助

作者简介: 通讯作者:刘海弟

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https://www.cjmr.org/CN/10.11901/1005.3093.2015.088 或 https://www.cjmr.org/CN/Y2016/V30/I2/123

表1 不同金属离子负载所得样品的比表面,平均孔径和累积孔容

图1 样品的XRD谱

图2 样品在100-300℃范围内的催化效果曲线

图3 样品的H2-程序升温还原曲线

图4 样品的NH3-程序升温脱附曲线

图5 各样品中过渡金属元素的2p XPS谱图

图6 各样品中Ce元素的3d XPS谱图

图7 样品Cr-Zr-Ce,Mn-Zr-Ce和V-Zr-Ce的耐硫性

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